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Kinetic and Theoretical Study of the Atmospheric Aqueous-Phase Reactions of OH Radicals with Methoxyphenolic Compounds
- Source :
- The journal of physical chemistry. A. 123(36)
- Publication Year :
- 2019
-
Abstract
- Methoxyphenols, which are emitted through biomass burning, are an important species in atmospheric chemistry. In the present study, temperature-dependent aqueous-phase OH radical reactions of six methoxyphenols and two related phenols have been investigated through laser flash photolysis and the density functional theory. The rate constants obtained were in a range of (1.1-1.9) × 1010 L mol-1 s-1 with k(3-MC) > k(Cre) ≈ k(Syr) ≈ k(MEP) > k(Res) > k(3-MP) > k(2-EP) ≈ k(2-MP). We derived the parameters of these reactions from the obtained T-dependent rate constants and found a mean Arrhenius activation energy of 16.9 kJ mol-1. The diffusion rate constants were calculated for each case and compared to the measured ones. Generally, the rate constants are found to be close to fully diffusion-controlled (kdiff = (1.4-1.5) × 1010 L mol-1 s-1 for all reactions). A structure-function relationship was established through the measurement result, which could be used for predicting unknown rate constants of other phenolic compounds. All of these findings are expected to enhance the predictive capabilities of models, such as the chemical aqueous-phase radical mechanism.
- Subjects :
- Arrhenius equation
010304 chemical physics
Chemistry
Radical
Analytical chemistry
Activation energy
010402 general chemistry
Kinetic energy
01 natural sciences
7. Clean energy
0104 chemical sciences
symbols.namesake
Reaction rate constant
13. Climate action
Atmospheric chemistry
0103 physical sciences
symbols
Flash photolysis
Density functional theory
Physical and Theoretical Chemistry
Subjects
Details
- ISSN :
- 15205215
- Volume :
- 123
- Issue :
- 36
- Database :
- OpenAIRE
- Journal :
- The journal of physical chemistry. A
- Accession number :
- edsair.doi.dedup.....45626442d0d6dc5d1964a0c5b081d49f